Hidetoshi Tomita, F. Sanda, T. Endo
Dec 1, 2001
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Journal
Journal of Polymer Science Part A
Abstract
This article deals with the polyaddition of a novel bis(seven-membered cyclic carbonate), 1,2-bis[3-(1,3-dioxepan-2-one-5-yl)-propylthio]ethane, with the diamines 4,9-dioxa-1,12-dodecanediamine and p-xylylenediamine. The polyaddition was carried out at 30–70 °C for 6–24 h in dimethyl sulfoxide to obtain the corresponding polyhydroxyurethanes with number-average molecular weights of 10,900–35,700 in good yields. The reaction of a monofunctional seven-membered cyclic carbonate, 5-allyl-1,3-dioxepan-2-one (7CC), with monoamines was also carried out to examine the reactivity in comparison with that of six- and five-membered cyclic carbonates. The reaction rate constants of 7CC with n-hexylamine and benzylamine were estimated to be 48.5 and 11.0 L/mol · h, respectively, in dimethyl sulfoxide-d6 (initial reagent concentration = 1 M) at 30 °C. The seven-membered cyclic carbonate ring was 2.98 and 5.82 kcal/mol more strained than those of the six- and five-membered cyclic carbonates, respectively, according to a semiempirical molecular orbital calculation with the PM3 Hamiltonian. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4091–4100, 2001